DE1926506B2 - Process for making crimpable viscose rayon of high wet modulus - Google Patents

Description

age.

35 SIo is z. B. in the Austrian patent 2 50 553 a process for the production of crimped

The invention relates to a method for tem viscose rayon described, wherein a viscose

Manufacture of crimpable viscose rayon of mil: a content of a zinc compound and of

high wet modulus by spinning a viscose, polyethylene glycol in a sulfuric acid sulfate spinning

which is simultaneously a modifier and a 40 bath at a salt point of 3 to 14 spun that

Contains zinc compound, contained in a zinc sulfate- resulting non-regenerated fiber by more than

of the sulfuric acid sulfate type spinning bath. 50% stretched, then relieved of tension and in

Viscose rayon was previously an aqueous sodium hydroxide solution with regard to water,

resistance and alkali resistance unsatisfactory. The fiber obtained has a frizzy value of

and as a result, the dimensional stability 45 was about 3 to 4 cm, but a wet strength and elongation

of substances made using viscose cleaning, which is closely related to the 5%

were made, bad. Values of as low as about 1.2 to

various methods of eliminating these drawbacks from 1.3 g / den or as high as 35 to 50%. if

suggested that the wet strength is low and the wet elongation is low in the following three groups

can be classified: 50 is high, only a low 5% N.M. value is allowed

In the first method, viscose rayon is made under expected due to the fact that the previous use of a modifier is made. Regular type viscose rayon materials such as Although in this method the water resistance wet strength of about 1.5 g / den and wet elongation and alkali resistance are satisfactory, they have only 5% NM sitting of about 25 to 30% obtained fibers poor spinning quality. 55 have a value of below about 0.3 g / den.
As a result, the production capacity is impaired. In German patent specification 1122 214, processes for the production of crimped viscose light fibrils are also formed in the fibers obtained in this way. reyon yarn, whereby one with poly- (oxy-

According to the second procedure, formaldehyde (ethylene) glycol is added to viscose in a spinning bath

used as a modifier, similar 60 containing 1 to 2% zinc sulfate at one

Advantages and disadvantages as with the first working method salt point from 3 to 14 spun and the resulting

available. The remaining fiber is stretched by at least 60% and

According to the third procedure, amines or the pressure is then released in the usual way. the

Derivatives thereof used as modifiers, fiber obtained by this process also has

with that of the aforementioned first and second 65 if a low 5% N.M. value and a poor one

disadvantages related to water and alkali resistance,

on the spinning quality and the fibril formation in the object of the invention is therefore to create one

essential to be overcome. However, the process for making crimpable viscose

3 4

of high wet modulus, at which the pre-crystallization level differs from that of fibers which

The disadvantages described were essentially obtained with different modification means

'' S! D, however, is the degree of orientation of the entire

!earth

under investigation for making fibers possess high durability, water-ÜüüändifiJcei't and alkali resistance, do not form ^ -Ilen and give a good grip on hieraas frtieten Türhern, has now been found, ll "fibers ihaften with good properties in terms of Γ Formation of fibrils water-resistant

with different modification means however, the degree of orientation of the entire fibers is as determined by birefringence measurements is obtained, and the degree of orientation of the crystal parts, obtained by X-ray measurement is large, and the degree of orientation is amorphous

The free part, which is calculated from these values, is a particularly large fiber with good properties. The properties of the fibers depend on the properties of the amorphous parts, including the formation of fibrils and water resistance. Therefore, alkali resistance and other properties are believed to result in the improvement of the intrinsic curling ability, which the amorphous parts have not yet obtained in close relation to the

Improvement of the properties of the overall fibers are available. Thus, because of the Orientieningsgrad amor- ^ ^ ^. ^ ^^ ^ ^ _{Improvement g th e}

Properties of the amorphous TeUe, which largely ^ to contributes to the wet modulus at 5% elongation, whichever is the criterion for water resistance and the Alkali resistance as well as the strength of the fiber is. As already stated above, the viscose rayon obtainable according to the invention shows good clamping properties ifld d extent of homosexual

? wft alkali resistance and other properties v Ability to pucker as it has not been obtained before were able to use a combination

* ™ T obtained from modifiers are naüon from m

rlmk of the invention, a method for the α «slening of crimpable viscose rayon from ShTm wet module is created, which is characterized by

• wt is that you use a viscose that

* "Salt point below 7 and a y-value» o vlTwemger than 57, which is caused by xanthogenic

• Zl with 29 to 35 percent by weight of sulphurous matter based on cellulose "has been obtained

• t and the a) one or more aliphatic or the fibers obtained do not contain any abnormal Vdic monoamines with 1 to 6 carbon atoms * 5 fibers and other impuritiesι and ze.gene.ne

oSr alkylene oxide derivatives of these aliphatic or good tensile strength and good anti-fibrous properties Monoamines, b) one or more zincs as well as good water resistance and hb

They are dehydrated in sodium hydroxide or water. As a result, the ^Οι ^ ^η51 ° ^η V percent by weight are soluble, as well as cloths made therefrom or

viscose rayon availability, so that as a result the extent of homo-

The genization of the obtained fibers is very high and the obtained fibers do not contain any abnormal ones Viund ze.gene.ne

Shnet as zinc -, and that the viscose in a The invention is below with reference to the

Shr as! Percent by weight zinc sulfate containing 35 drawing near ^^^ η enlarged photographi- ? n that by using see sectional images of fibers. Fi g ^ represents a

"STdSS. Use de,

2 ^

moderate cross-sectional shape, wöbe, the entire Faseln da to ~ regenem ^ ^ ^^

essentially a circular small projection queUwerjJjes ^ acn _regeneration th yarn and B to

own, and due to this asymmetrical ^ te ^ n tolwe ^ reg. ^^^. ^^^

The crimpability results from the cut. An 55 ^^^ "^ / ^" "", ^ η partially regenerated cooking

on the other hand, in the case of the application of the previous rules, an active _{relationship is established}

has not yet been clarified. However, it was confirmed that in the training of such specific !: cuts unique properties in terms of coagulation, Dehydration and regeneration during

^{NaD module at}

_stated , the conversion in the modifier must be soluble in sodium hydroxide or % by weight.

_Lö "» e ", we, ede,

V «t»

fertilize can be used, although favorably but must in the specified according to the invention

a connection is in use. The effect is a combination of one or more zinc compounds

not improved if two or more compounds fertilize and one or more amine compounds

can be used. can be used together, since on the other hand the

The timing of adding the zinc compounds 5 effects described above were not obtained

is not particularly critical. Preferably they will be

however, added just before spinning. The amount of carbon disulfide in the Xan

If the zinc compound or the zinc compound thinning is between more than 29% and less

gen in an amount less than 0.1 percent by weight than 35%, based on cellulose, in particular 30 to

are used, the combination effect of the io becomes 34%. If the amount is less than 29%,

Zinc compound with the amine compound and the properties of viscose deteriorate, and

if necessary the polyethylene glycol worsens, if the amount is more than 35%, worsen

rend when adding the zinc compound in a 10 gel, the properties of the fibers obtained,

The viscosity of the viscose is conveniently no additional amount exceeding weight percent

Improvement is achieved. Preferably the 15 will be 50 to 400 seconds. If the viscosity is low,

Zinc compound in an amount of 1 to 5 weight- it can be used by the conditions

Percent, based on cellulose, added. Since the can be set so that a high acid or

The main part of the added zinc compounds is obtained in sodium sulfate content. However it will

the dope dissolves during spinning, the host is preferred, an area outside of the above

economic load when adding the zinc in the 20 range with regard to the spinning properties and

Spinning solution low. on economic grounds to avoid.

The amine compounds that can be used are aliphatic. The degree of ripening of the viscose corresponds to one

Table or cyclic monoamines with 1 to 6 carbon salt points below 7 and a y value of

Atoms or alkylene oxide derivatives thereof. If below 57 and may according to the degradation

Amines with 7 or more carbon atoms used 25% of the acidity and sodium sulfate content in the

their combination effect with the spinning solution decreases by lowering the salt point and

Zinc compounds and optionally the poly of the γ value can be adjusted. If salt point and

ethylene glycol noticeably. Furthermore, the combination y value is higher than 7 or 57, which is worse

national effect of the amines with the zinc compounds, the spinning properties, and also the orientation

and the polyethylene glycol is superior to the 30- 30 effect when stretching is unfavorable, and further

those of the alkylene oxide derivatives. Examples of this are shown by the wet modulus at 5% elongation, which is the

like amine compounds are monomethylamine, criterion for water resistance and alkali

Dimethylamine, diethylamine, propylamine, cyclohexyl resistance of the fibers obtained is a tendency

amine and butylamine and derivatives thereof, which are about to lower.

Contains 3 mol of ethylene oxide added. These amine modifiers can be used individually or in the form of less than 60 m / min. If the spinning speed of mixtures of two or more used is too high, abnormal fibers are easily formed,
will. If two or more modes are used, the length of the first bath is preferably smaller, but the effect will not increase any more than 10 cm. If the bath is too short, it is better. 40 manoeuvrable, facilities for regulating coagulation

The time of addition of these modifiers to the dehydration and the regeneration

is not subject to any particular restriction, they will see, until the stretching takes place, what as a result

however, preferably added just before spinning. not particularly because of the complicated steps

The amount of the amine listed above is favorable.

compounds is more than 0.1%, based on 45 The acid concentration in the first bath is

Cellulose. If two or more compounds, preferably less than 7%. The cheapest concentrate

are used, the total amount is more than tration, depending on the degree of ripeness of the

0.1%. If less than 0.1% is used, viscose, the viscosity, the percentage of cellulose

the cooperative effect of the same with the and the percentage of alkali in the viscose is

Zinc compounds and possibly the poly 50 is correct. If the percentage of alkali in the viscose

Ethylene glycol is bad, and if more than 10% is tensile, the favorable condition is often more than

the interacting effect will be 7% acid concentration. However, that should be avoided

no longer improved. One will be preferred because the wet modulus has a slope at 5%

Amount used from 0.5 to 4%. shows less waste and more economical

With regard to the polyethylene glycol, there are disadvantages in this case. The group owners Molecular weight 800 to 1700. Here, too, the sodium sulfate tration is preferably less no restriction on the amount of additive than 12%, which depends on the acid concentration Time, however, the addition is preferably short. In this case, if the alkali concentration in the before spinning. The amount of additive is viscose is very high, the most favorable condition is over 0.1%, based on cellulose. If less than 60, often more than 12%. However, this should come from the same 0.1% is used, the interacting reasons as with the acid concentration are different the same with the zinc compounds and the be avoided.

Amine compounds poor, and if more than 10% The concentration of zinc sulfate in the first used, the cooperative bath is more than 1%. If less than 1% before effect not further improved. Preference is given to a 65 hand, abnormal fibers are formed, nozzles Amount used from 0.3 to 3%. clogged and the spinning properties extremely

The three bad modifications described above, and it still does not become effective

agents cannot be used on their own, to obtain orientation of the fibers during stretching, and

the properties of the fibers deteriorate. If the concentration is higher, the loss will pass through Splash too. Therefore, the concentration of zinc sulfate is preferably 3 to 5%.

The temperature of the first bath is preferably from 20 to 50 ^° C., depending on the thermal economy or management.

The second bath is a regeneration bath with a low acid concentration and a high one Temperature is used in which the stretching is carried out.

example 1

A wood pulp having a degree of polymerization of about 800 was soaked in a 17.5% solution of Natriurahydroxyd at 20 ° C for 90 minutes, then squeezed out of the alkaline pulp to 2.7 times, based on dry pulp and 20 to 50 ⁰ C. frayed for 60 minutes. To the alkali cellulose obtained, 33% carbon disulfide based on alkali cellulose was added. After xanthogenation at 20 to 28 ° C for 120 minutes, 5% zinc acetate, 3% dimethylamine, 2% polyethylene glycol, dissolved in alkali and water, were added and a viscose containing 7% cellulose and 6% alkali by dissolving at 13 ° C maintained for 3 hours. The viscosity of the viscose obtained was 280 seconds.

After filtering and ripening until the viscose had a salt point of 5.9 and a y value of 51, the viscose was washed at 30 m / min using the first bath, which contained 5% sulfuric acid, 7% sodium sulphate and 4% zinc sulphate and was at 40 ° C, spun and then stretched to 190% using the second bath. Thereby, the fiber A was obtained after refining and drying by known methods. Fiber B was produced under the same conditions but using the same amounts of dimethylamine and polyethylene glycol. Fiber C was made under the same conditions but using only the same amount of zinc acetate. Fiber D was made under the same conditions but using the same amount of zinc acetate and polyethylene glycol. The characteristics of this

ίο Fibers are listed below. Thereby means the indication of 5% NM in the tables and examples the wet modulus at 5% elongation, and the Crimp number indicates the number of crimps that develop when a 10 cm length is cut Yarn bundle is drawn after stretching in water of normal temperature.

Furthermore, the values of typical fibers on the market are high for comparison Wet modulus specified.

Ao enlarged sectional images of the fiber according to the invention and the fiber 5 according to the prior art are shown in FIGS. 1 and 2 shown. The fiber B has a circular section, while the fiber A according to the invention has an asymmetrical circular

shows a5-shaped section with a slight protrusion. Furthermore, in the F i g. 3 and 4 the remaining y values and the gel swell values of the partially regenerated yarns, which were formed by changing the acid concentration of the first bath in the manufacture of fibers A and B , are shown. The partially regenerated yarn of fiber A according to the invention gave a high residual y value at all acid concentrations and a low gel swell value at the same y value compared to the partially regenerated yarn of fiber B, showing that the fibers according to the invention have good stretch properties and orientation properties.

Table I.

denier Dry Dry Wet Wet node 5% N.M. Orientie Krause strength strain strength strain strength degree of efficiency lungs number UCl dXllUl ■ "
phen parts (g / d) (%) te / d) (%) fe / d) (g / d) (%) (Number/
10 centimeters) A. 1.5 5.6 10 4.0 11th 2.6 1.5 40 12th B. 1.5 4.4 15th 2.9 18th 2.3 0.6 34 0 C. 1.5 2.6 11th 1.6 13th 1.6 0.6 25th 0 D. 1.5 3.0 10 2.1 11th 1.6 0.8 27 3 * 1.5 4.6 15th 3.2 16 2.2 0.7 - -

·) Fiber on the market.

Example 2

To an alkali cellulose prepared by the same process as in Example 1, 34% carbon disulfide was added and the xanthogenation was carried out at 20 to 23 ° C. for 120 minutes. Then, 4% cyclohexylamine, 4% sodium zincate, and alkali and water to dissolve were added, whereby a viscose containing 7% cellulose and 6% alkali was obtained. After filtering and deaerating, ripening was carried out until the viscose had a salt point of 6.5 and a y value of 53. The viscosity of this viscose was 180 seconds. This viscose was with 30 m / min

509 549/366

spun using the first bath containing 6% sulfuric acid, 10% sodium sulfate and 4% zinc sulfate and had a temperature of 35 ° C, and then stretched to 150% in the second bath. Then the fiber was refined and dried and

10

fiber A is thereby obtained. A fiber B was produced under the same conditions, except that only the same amount of cyclohexylamine was used. The properties of these fibers are listed in the table below.

Table II

denier

Dry strength

(g / d)

Dry stretch

Wet strength

(g / d) Wet stretch

Knot strength

(g / d)

5% M. N.

(g / d)

Curl number (Number / 10cm)

1.5
1.5

4.8 4.0

12th
15th

3.4 15th 2.3 1.0 25th 2.7 18th 2.1 0.6 0

Example 3

To an alkali cellulose produced by the same process as in Example 1, 32% Carbon disulfide added and the xanthogenation carried out at 20 to 28 ° C for 120 minutes. Then 3% _ of a compound obtained by adding 3 moles of ethylene oxide to butylamine 4% zinc acetate, 4% polyethylene glycol and alkali and water to dissolve had been added and obtained a viscose with a content of 7% cellulose and 6% alkali. After filtering and venting ripening was carried out until the viscose had a salt point of 5.5 and a y value of 48. the The viscosity of this viscose was 220 seconds. the

ao obtained viscose was applied at 35 m / min a first bath spun which contains 5% sulfuric acid, 5% sodium sulfate and 4% zinc sulfate and was at 35 ° C, followed by 155% stretching in the second bath. then

the fiber was refined and dried to obtain fiber A. A fiber B was produced under the same conditions, but using only the same amount of the compound formed by the addition of 3 mol of ethylene oxide to butylamine and

Polyethylene glycol was used. The properties of the yarns are listed in the following table.

Table III denier Dry
strength
(g / d) Dry
strain
(%) Wet-
strength
(g / d) Wet
strain
(%) node
strength
(g / d) 5% NM
(g / d) Frizz
number
(Number / 10cm: 1.5
1.5 4.9
4.1 11th
13th 3.3
2.8 13th
16 2.4
2.0 1.1
0.6 20th
0 A.
B.

Example 4

The viscosity of this viscose was 350 seconds. This viscose was measured at 30 m / min using a

Game 1 produced alkali cellulose., _, _{/ o} carbon disulfide was added and the xanthogenation was carried out at 20 to 28 ° C for 120 minutes. Then 3% dimethylamine, 5% zinc sulfate, 2% polyethylene glycol and alkali and water to dissolve were added, whereby a viscose containing 7% cellulose and 6% alkali was obtained. After filtration and deaeration, ripening was carried out until the viscose had a salt point of 6.0 and a y value of 52. The .. uuu ^ js «-s ^ uiiucu, weiunes t / ό ocnwcicisaui« -

Containing 8% sodium sulfate and 4% zinc sulfate and having a temperature of 35 ° C, whereupon the Strecker ran to 170% in the second bath. The fiber was refined and dried and in doing so the Get fiber.

A fiber I was produced under the same conditions, except that only the same amount of ar dimethylamine and polyethylene glycol was used. The properties of the yarns are listed in the table below.

Tabel TV Dry
strength
(g / d) Dry
strain
(%) node
strength
(g / d) 5% M. N.
(g / d) Ripple
(Number / 10 cm) denier 5.5
4.3 11th
113 2.4
2.0
1.4
0.8 13th
0 A.
B. 1.5
1.5

In the F i g. 5 and 6 the dry strength and the wet modulus at 5% elongation of fibers are plotted, that by spinning and stretching under the same conditions, but with a change in the Amount of carbon disulfide used to xanthate the alkali cellulose.

It results from this that very high strengths wet modulus values with a lot of sulfur feces substance in the range of 29 to 35% were obtained that the spider properties in this range av s draws were.

For this purpose 2 sheets of drawings

Claims (2)

1 2 Water resistance and alkali resistance not in patent claims: Improved to a sufficient extent, which is achieved through the contraction of the substances made from them 1. Indicates method of making shirring wash. Viscose rayon of high wet modulus by means of 5 It can thus be seen that the known working spinning of a viscose, which at the same time has a modification using modincing agents, As mentioned above, contains a dressing agent and a zinc compound in terms of improvements a spinning bath containing zinc sulphate does not yet have the properties of viscose rayon Sulfuric acid sulphate type, which means that they are satisfactory. draws that a viscose is used, ι » As described above, the previously used has a salt point of below 7 and a known viscose rayon has the disadvantage of an insufficient y value of less than 57, which is due to water and alkali resistance and also in xanthogen with 29 to 35 percent by weight of the form of fabric, poor dimensional carbon disulfide based on cellulose maintains stability. The poor water and alkali resistance has been, and the a) one or more accuracy can be improved by adding the wet phase or cyclic monoamines with 1 to strength and elongation, in particular the wet modulus 6 carbon atoms or alkylene oxide derivatives at 5 % Elongation (also hereinafter referred to as 5% NM-these aliphatic or cyclic monoamines, value) improved. However, b) one or more zinc compounds which, in improving the 5% NM value, are disadvantageously soluble in sodium hydroxide or water to more than the behavior of the fiber in relation to other intrinsic 0.05 percent by weight, as well as, In particular, the crimping ability, essentially c) contains polyethylene glycol, and that is impaired. a), b) and optionally c) each in an amount. On the other hand, the crimpability is more similar of more than 0.1 percent by weight, based on fibers, a particularly important property, and the Cellulose - but in the case of the zinc compound 35 textile goods made from it, such as fabrics, blankets, Calculated as zinc -, and that you use the viscose carpets, non-woven fabrics or the like, are accordingly in more than 1 percent by weight of zinc sulphate - provided with excellent properties, holding spinning bath spun. Although so far a number of procedures for the 2. The method according to claim 1, characterized in the production of viscose rayon yarns with a curl, that one was known to be a polyethylene glycol with a 3o selbarkeit, but have the after Molecular weight from 800 to 1700 used. such previously known methods produced Viscose rayon crimped yarns have a low 5% N.M. value and a poor water and alkali resistance